Polynitro esters



POLYNITRO ESTERS Milton B. Frankel, Pasadena, Calif assignor to Aerojet- General Corporation, Azusa, Calif., a corporation of Ohio No Drawing. Filed June 20, 1955, Ser. No. 516,794

22 Claims. (Cl. 260-482) This invention relates to new compositions of matter and a method for their preparation. In particular, it relates to polynitro esters having the general formula:

wherein X is a polynitroalkylene or nitraza-alkylene radical and R and R are nitroalkyl radicals.

The nitro compounds of this invention are useful as high explosives and can be used in any conventional explosive missile, projectile, rocket, or the like, as the main explosive in powder form into the warhead of the missile. closed in United States Patent No. 2,470,162, issued May 17, 1949. One way of using the high explosives of this invention in a device such as that disclosed in United States Patent No. 2,470,162, is to pack the crystalline explosive in powder from into the warhead of the missile. Alternatively, the crystals can be first pelletized and then packed. A charge thus prepared is sufi'iciently insensitive to withstand the shock entailed in the ejection of a shell from a gun barrel or from a rocket launching tube under the pressure developed from ignition of a propellant charge, and can be caused to explode on operation of an impactor time fuse-mechanism firing a detonating explosive such as lead azide or mercury fulminate.

The new compositions of matter of this invention are prepared by condensing nitro acids or acid halides with nitro alcohols, in accordance with the general reaction scheme set forth below:

X are as defined above.

As a matter of convenience in obtaining better control and smoothness of the reaction, the reaction is usually conducted in the presence of an inert organic solvent such as ethylene dichloride or chloroform.

To more clearly illustrate this invention, the following examples are presented. ever, that these examples are presented merely as a means of illustration and are not intended to limit the scope of the invention in any way.

EXAMPLE I Preparation of bis (2 ,2,2-trinilrethyl -4,7-dinitraza- 1,10-decanedioate In a 100 ml. round-bottom flask, fitted with a condenser and drying tube, was placed a solution of 3.62 gm. (0.02 mole) of 2,2,2-trinitroethanol, in 50 ml. of dry ethylene dichloride. Anhydrous aluminum chloride, 0.27 gm. (0.002 mole), was added and the solution turned yellow. To the solution was added 3.31 gm. (0.01 mole) of 4,7-dinitraza-1,10-decanedioyl chloride. The reaction mixture was refluxed until evolution of hydrogen chloride gas had ceased. The black mixture was cooled and filtered, the solid was washed with cold It should be understood, how-.

dilute hydrochloric acid, water, dried, and recrystallized from ethylene dichloride using charcoal to give 5.3 gm. (85.5%) of white crystals, M.P. 126-128" C. Elemental analysis of the product was as follows:

Calculated for C H N O 'PercentC, 23.23;. percent H, 2.60; percent N, 22.58. Found: Percent C, 23.49; percent H, 2.90; percent N, 23.10.

EXAMPLE II 1 Preparation of bis(2,2,2-trinitroethyl-4,4,6,6,8,8-hexanitr0-1,1I-undecanedioate In a 500 ml. Erlenmeyer flask was placed gm. of 100% sulfuric acid, 18.0 gm. (0.1 mole) of 2,2,2-trinitroethanol, followed by 24.3 gm. (0.05 mole) of 4,4, 6,6,8,8-hexanitro-1,1l-undecanedioic acid and 50 ml. of chloroform. After standing for five days with occasional shaking, the copious white solid was collected, washed with ice-water, and dried, 35.6 gm. (87.8%), M.P. 114- 116 C. Recrystallization from chloroform raised the melting point to 117118 C. Elemental analysis of the product was as follows:

Calculated for C H N O percent C, 22.18; percent H, 1.99; percent N. 20.69. Found: percent C, 22.06; percent H, 1.94; percent N, 20.88.

EXAMPLE III Preparation of bis(2,2,2-trinitr0ethyl)-3,6-dinitraza- 1,8-0ctanedi0ate Calculated for C H N O percent C, 20.28; percent H, 2.04; percent N. 23.65. Found: percent H, 2.34; percent N, 23.73.

EXAMPLE IV Preparation of bis(2,2,2-trinitr0ethyl)-4,4-dinitr0- 1,7-heptanedi0ate In a 100 ml. round-bottom flask, fitted with a condenser and drying tube, was placed a solution of 3.62 gm. (0.02 mole) of 2,2,2-trinitroethanol, in 50 ml. of dry ethylene dichloride. 0.27 gm. (0.002 mole), was added and the solution turned yellow. To the solution was added 2.87 gm. (0.01 mole) of 4,4-dinitro-1,7-heptanedioyl chloride. The reaction mixture was refluxed until evolution of hydrogen chloride gas had ceased. The black mixture was cooled and filtered, the solid was washed with cold dilute hydrochloric acid, Water, dried and recrystallized from ethylene dichloride using charcoal to give 2.7 gm. (47.0%) of white crystals, M.P. -l71 C. Elemental analysis of the product was as follows:

Calculated for C H N O percent C, 22.93; percent H, 2.10; percent N. 19.45. Found: percent C, 23.18; percent H, 2.09; percent N. 18.74.

EXAMPLE v Preparation of. bis(2,2,2-trinitr0ethyl)-4-nitrazz- 1,7-heptanedioate In a 100 ml. round-bottom flask, fitted with a condenser and drying tube, was placed a solution of 3.62gm,

percent C, 20.49;

Patented Apr. 4, .1961

Anhydrous aluminum chloride,

2,978,494 3 4 (0.02 mole) of 2,2,2-trinitroethanol, in 50 ml. of chloroin the practice of my invention are preferably conducted form. Anhydrous aluminum chloride, 0.27 gm. (0.002 in the presence of AlCl mole), was added and the solution turned yellow. To It is apparent from the above discussion that the entire the solution was added 2.06 gm. (0.01 mole) of 4-niseries of polynitro esters, having valuable use as high traza-l,7-heptanedioyl chloride. The .reaction mixture 5 explosives can be prepared by merely condensing an apwas refluxed until evolution of hydrogen chloride gas propriate nitro acid with a nitro alcohol. had ceased. The black mixture was cooled and filtered, The acids used as starting materials in this invention are the solid was Washed with cold dilute hydrochloric acid, obtained by hydrolyzing the corresponding nitriles, as diswater, dried and recrystallized from chloroform using closed in assignees copending application Serial No. charcoal to give 1.91 gm. (35.9%), of white crystals, 438,296, filed June 21, 1954, now abandoned, or by hy- M.P. 11011l C. Elemental analysis of the product drolyzing their corresponding alkyl esters, as disclosed in was as follows: assignees copending applications Serial No. 392,479, filed Calculated for C H N O percent C, 22.56; per- November 16, 1953, now abandoned, and Serial No. cent H, 2.27; percent N, 21.05. Found: percent C, 22.58; 198,491, filed November 30, 1950, now Patent No. percent H, 2.26; percent N, 20.93. 2,918,489. The acid halides are obtained by reacting the EXAMPLE VI nitro acids with thionyl halide.

I claim: Prepamfia" f M y Z 'P 1. As compositions of matter, polynitro esters having tanedioate the general formula: In a 500 ml. round-bottom flask, fitted with a reflux con- 20 denser and drying tube, was placed 10.75 gm. (0.05 mole) of 3-nitraza-1,5-pentanedioy1 chloride, 18.1 gm. (0.1 mole) of 2,2,2-trinitroethanol, 200 ml. of dry chloroform, and 6.6 gm. (0.05 mole) of anhydrous aluminum chloride. The mixture was refluxed for 1.5 hours, cooled to -20 C., and filtered. The cream-colored solid was washed with cold 6N hydrochloric acid and water, and dried. 19.6 gm. of product were obtained melting at 146150 A LN RO-OXCO--R wherein X is a radical selected from the group consisting of polynitroalkylene and nitraza-alkylene radicals and R and R are lower nitroalkyl radicals.

2. As compositions of matter, polynitro esters having the general formula:

0: O C. Recrystallization from ethylene dichloride gave a P white crystalline solid, MP. 160-1605 C. Elemental Jx analysis of the product was as follows: where R and R are lower nitroalkyl radicals, A and A Calculated for C H N O percent C, 19.06; percent H,

are lower alkylene radicals and x is a small whole number 1.60; percent N, 22.23. Found: percent C, 19.40; percent from 1 to 6 inclusive.

H, 2.00; percent N, 22.34. 3. As compositions of matter, polynitro esters having I have also found that by proceeding in accordance the general formula:

with the method set forth in the above examples, that 4,4- 0 N01 0 dinitro-1,7-heptanedioic acid condenses with 2,2-dinitro- 1 1 ll propyl alcohol to produce bis(2,2-dinitropropyl)-4,4-di- T? T nitro-1,7-heptanedioate; 4-nitro-1,7-heptanedioic acid con- 40 NO:

(1611865 With 2,2,2-tl'l1'1ltl0fithj/l alcohol t0 produce 1918- wherein R and R are lower nitroalkyl radicals A and A l 1,7 heptanedioate; a11d are lower alkylene radicals and x is a small whole number nitraza-1,7-heptanedioic acid condenses with 2,2-dinitrofro 1 t 6 i l i propyl alcohol to produce bis(2,2-dinitropropyl)-4 4. As a composition of matter, bis(2,2,2-trinitroethyl)- nitraza-1,7-heptanedioate. 4,7-dinitraza-1,10-decanedioate having the structural The dibasic acids used in my invention can be of any formula:

N0: 1'90: 1Y0: 1Y0: NOr-+-CHr-O-C-CH:CHzNCHzCHr'NCH:CHg-CO-CH:?NO;

chain length desired and can contain any number of gem- 5. As a composition of matter, bis(2,2,2-trinitroethyl)- dinitro or nitraza groupings. Thus, such acids as 4,4,6,6,8,8-hexanitro 1,11 undecanedioate having the 4,6,8,10-tetranitraza-tridecane-l,13-dioic acid, 4,6,8,10,- structural formula:

12,14-hexanitraza-heptadecane 1,17 dioic acid, 4,4,6- A a mp n of m t y 6,8,8,10,10,12,12,14,14 -dodecanitro-heptad can 1 17. 4,4-dinitro 1,7 -heptanedioate having the structural dioic acid, 4,4,6,6,8,8,10,10-octanitro-tridecane-1,13-dioic 5 formula:

acid, etc., can also be used in the practice of this inven- 1110, (a IfOr O NO;

II NOz-C-CHz-O C-CHzCHz-C-CHzCHz-C-O-CHz-CJVO:

Mixed esters can be produced by employing a mixture l 1 NO; NO; N0;

of nitro alcohols in the condensation reaction disclosed.

In the preparation of the new compounds of this invention, I have found that the yields obtained are con- 7. As a composition of matter, bis(2,2,2-trinitrocthyl)- 4-n1traza 1,7 heptanedioate having the structural siderably increased when the reactions are conducted in formula:

the presence of certain catalysts. Thus it is preferred to 7 g conduct reactions utilizing free acids in the presence of NOrC-CHz-O-C-C 2CHrN-CHaCH2C'OCHrC-NO: sulfuric ac1d or oleum. Reactions of acid halides 8. As a composition of matter, bis(2,2,2-trinitroethy1)- 9. As a composition of matter, bis(2,2,2-trinitroethyl)- 3-nitraza-l,S-pentanedioate having the structural formula:

10. As a composition of matter, bis(2,2-dinitropropyl)- 4,4-dinitro-1,7-heptanedioate having the structural formula:

11. As a composition of matter, his(2,2-dinitropropyl)- 4-nitraza-l,7-heptanedioate having the structural formula:

12. The method of preparing polynitro esters having the general formula:

R-OCXGO-R which comprises reacting a lower nitroalkanol with an acid having the general formula:

HO-C-X-C-OH wherein R and R are lower nitroalkyl radicals and X is a radical selected from the group consisting of polynitroalkylene and nitraza-alkylene radicals in the presence of a catalyst selected from the group consisting of 100% sulfuric acid and oleum.

14. The method of preparing polynitro esters having the general formula:

which comprises reacting a lower nitroalkanol with an acid halide having the general formula:

o o Z('7X-i')-Z wherein R and R are lower nitroalkyl radicals, X is a radical selected from the group consisting of polynitroalkylene and nitraza-alkylene radicals and Z is a halogen radical in the presence of AlCl 15. The method of preparing bis(2,2,2-trinitroethyl)- 4,7-dinitraza-1,lO-decanedioate which comprises reacting 2,2,2,-trinitroethyl alcohol with 4,7-dinitraza-1,IO-decanedioyl chloride.

16. .The method of preparing bis(2,2,2-trinitroethyl)- 4,4,6,6,8,8-hexanitro-l,1l-undecanedioate which comprises reacting 2,2,2-trinitroethyl alcohol with 4,4,6,6,8,8- hexanitro-1,1l-undecanedioic acid.

17. The method of preparing bis(2,2,2-trinitroethyl)- 3,6-dinitraza-l,8-octanedioate which comprises reacting 2,2,2-trinitroethyl alcohol with 3,6-dinitraza-L8-octanedioyl chloride.

18. The method of preparing bis(2,2,2-trinitroethyl)- 4,4-dinitro-1,7-heptanedioate which comprises reacting 2,2,2,-trinitroethyl alcohol with 4,4-dinitro1,7-heptanedioyl chloride.

19. The method of preparing bis(2,2,2-trinitroethyl)- 4-nitraza-l,7-heptanedioate which comprises reacting 2,2,2-trinitroethyl alcohol with 4-nitraza-1,7-heptanedioyl chloride.

20. The method of preparing bis(2,2-dinitropropyl)- 4,4-dinitro-1,7-heptanedioate which comprises reacting 2,2-dinitropropyl alcohol with 4,4-dinitro-1,7-heptane dioyl chloride.

21. The method of preparing bis(2,2-dinitropropyl)- 4-nitraza-1,7-heptanedioate which comprises reacting 2,2- dinitropropyl alcohol with 4-nitraza-l,7-heptanedioyl chloride.

22. The method of preparing bis(2,2,2-trinitroethyl)- 3 -nitraza-l,5-pentanedioate which comprises reacting 2,2,2-trinitroethyl alcohol with 3-nitraza-1,5-pentanedioyl chloride.

References Cited in the file of this patent- UNITED STATES PATENTS 2,404,688 Bruson et al July 23, 1946 2,528,928 Weisblat et al Nov. 7, 1950 FOREIGN PATENTS 698,138 Great Britain Oct. 7, 1953 OTHER REFERENCES B.I.o.s., Final Report No. 709, item No. 22. The Production of Tetronitromethane and Nitroform, report by W. Hunter 3d, July 1946, page 8. 

1. AS COMPOSITIONS OF MATTER, POLYNITRO ESTERS HAVING THE GENERAL FORMULA: 